Direct azo dyes



Patented Aug. 11, 1931 WERNER. LARGE; or'n-EssAu-zrEBIeK m Ammnm, GERMANY, essrenon r0 I AmLrn-n worms; rue, or new YORK, N. y

A. CORPORATION i DELAWARE 'nmrzcr- -Azo DYES No Drawing; Application-filedOctober 3, 1929', Serial-Ro 397,1-514 ,;.amr1 imGnrmanyY October 10,1928? My present invention relates to new-azadyes and to a process of manufacturing thcnn Oneof its objects is: to provide direct dyesfor cotton and pigments, which are fast to the action; oii Light and to washing,

The: new dyes correspond probably to the, general formula V I have found that new dyes of the said qualitiesare obtainable by dia'zotizing a compound which correspondsto the general formula V ILN-R-J-INOC phenyl A phenyl QONH R NH wherein R represents a radicl'e of the group consisting of benzene, napthalene-, diphenyl-, stilbeneand diphenyl urearadicles" and of a plurality of ben zoylamino compounds of one of these radicles, linkedttogeth'er by an atomic linkage ofthe group con,- sisting of the azo1- and azoxy groupyand A represents a group consisting of'theaz-o or azoxy-group, and by coupling the bis-diazo compound, thus obtained, Wrth' anyazo com ponent.

' The starting material represented by the formula: given: aboveisobtalnabler-for in stance, by'a slight reduction ot'a nitrobenzoy lated aromatic amino compound containing inits moleculethe atomic group T Y RNH-GO' phenyl" N02, wherein R! represents an aromatic radicle-a-nd- Y stands for a substituent oi the gr0up consisting of N0 NIL, NHCO alkyl, N HCOaryl, N H'COarylN O WVater soluble dyestufis are" obtained, when start ing from a corresponding compound, in which the aromatic residue is substituted by a sul fon-i'c acid or carboxylic acid group.

The manufacture of-thesestartingmate; rials is not claimed in the present invention; it is the subject matter of U. S. application Ser. No. 340,654, filed by me and G. Kalischer as joint inventors on February 16,1929; Y The following examples "servefto illustrate my invention without limiting it to the specific details given therein, the parts being by weight v 4 Example 1.36.7 parts of sodium-l amino- 4- (4 nitrobenzoylamino) -benzen'e- 2- sulfonate of the formula 1 V HIN ONE-C OONO:

some I are dissolved in 1000 parts of water, At a temperature of 20 C. a: solution containing 4' parts of sodium hydroxide and 7.8'parts of anhydrous sodium sulfide is added, and the mixture is stirred until' thesulfide has disappeared. The yellow compound which has separated is filtered ofi? and purified by dis solving,in water andreprecipitating. t

32.1 parts of the product thus obtained are dissolved in 1000 parts ot wat'erQ To the solution are added successively 6.9 parts of} sodium nitrite and 50' parts of'hydrdchloric} acid o-t l2 B. ,The mixture is stirred for some hours at a temperature of'about 20 Cl until the diazotation; is complete. Then a solution of 25.4 parts of l-sulfophenyl-3- methyl-5-pyrazolone cooled by additionof ice and alkaline by carbonate is added.

The dye is finished in the usual manner. It forms in the dry state a yellowish powder Dyestuffs otsimilar qualities are obtainedthe presence ofsodium v which 1s soluble in water; from an aqueous the formula equivalent quantity of the when starting from a compound which is prepared by a slight reduction of l-amino-e (4-nitrobenzoylamino) -benzene-2-sulfonate with, for instance, glucose, arsenious oxide or zinc dust.

The dyestufl probably corresponds to formula the X represents either the azo groupN=N or the azoxy group a definite formula cannot be given, because it is uncertain, if by the slight reduction of Has-Omen OHNQ-NHC 004cm.

S6 Na 7 SOaNa The azodye prepared under the conditions given in Example 1 from the product; ob tainable by a slight reduction of this nitrobenzoyl compound has similar qualities as that described in the foregoing example. This dye probably corresponds to the general formula (ilaHrS OaNa wherein X may be the group N=N- or Example 3.-4L8.6 partslof 1.4-di-(4- nitrobenzoylamino) -benzene-2-sulfonic acid of are introduced, while stirring, into a hot mixtureof 500 parts of water, 33 parts of zinc dust and 10 parts of glacial acetic ac1d, and

the mass is then boiled for 5-10 minutes. The mixture is then diluted with 700 parts of water and made slightly alkaline with 12 parts of sodium carbonate. From the solution freed from zinc oxide the product separates on cooling.

A solution of 44.6 parts of the product thus obtained is prepared by heating with 1500 parts of water. After cooling to 20 0., 6.9

parts'of sodium nitrite and 50 parts of hydrochloric acid of 12 136.. are added and'the mixture is stirred for some hours. The diazotization finished, a cold solution of 25A parts of 1-sulfophenyl-3-methyl-5-pyrazolone which is made alkaline by the addition of sodium carbonate is added to the diazocompound. The dyestuff thus obtainedlis finished in the usual manner. It has qualities similar to that obtainable according to Example 1; cotton is directly dyed from an aqueous solution in somewhat greener shades.

Example .4.The diazo-compound obtainable, according to the conditions mentioned in Example 3 is reacted upon a cold solution of 17.7 parts of the anilide of acetoacetic acid which is alkaline by the presence of sodium carbonate. The dyestuff is finished in the usual manner, filtered off and pressed. Preferably it is worked up to form a paste. In this manner a beautiful yellow pigment is obtained.

Corresponding dyes are obtainable by coupling the diazo-compound with other azocomponents which provide yellow dyestufis, as for instance phenylmethyl-pyrazolone, dihydroxyquinoline, a-methylindole.

E mampZe.5.-The diazo-compound obtainable according tothe details given in Exame pie 3 is allowed to run into a solution of 38 parts of 2- (meta-amino-benzoylamino) -5- tized on the fiber and coupled with phenyL methylpyrazolone or ,B-naphthol, whereby the tints become fast to Washing without altering essentially the original shade.

I cannot give an exact formula of the dyestufis obtainable according to Examples 3-5,

because it is uncertain how many molecules of the starting material are linked together bythe reduction process. Probably, these dyes may be represented by the following general formula gether by an atomic linkage, of the group consisting of the, azoe and the azoxy, group,

I SO Na 7 $3M: v and; A represents an atomic linkage of the group conslstmg of 2. Th'enew direct azodyes for cotton correspondlng to: the general? formulaf sulfonic acid. As mentioned above, I am not sure Whether the products obtained by the slight reduction of the nitrobenzoylamino compound are linked together by the azo or the azoXy group. For the sake of greater clearness in the formula given above, I have inserted the azo group, however, it may be the azoxy' group. Furthermore, I do not know certainly how many molecules of the starting material are linked together by the slight reduction process. an therefore rep resents 0 or a whole number 1, 2, or, perhaps, a whole number greater than 3.

What I claim is gether by an atomic linkage of the group consisting of the azoand azoxy group, and A represents an atomic linkage of the group conslsting of N=N,

3. The new direct azo dyes for cotton corresponding to the general formula:

1. The new azo dyes corresponding to the general formula:

wherein the Zs represent the residues of any azo component, R represents a radicle of the group consisting of benzene, naphthalene, diphenyl-, stilbeneand diphenylurea rad1- cles and of a plurality of benzoylammo compounds of one of these radicles, linked towherein R represents a radicle of the group 4. The new dye, soluble in water and dyeing cotton directly in yellow shades of excellent fastness to light and to Washing and corresponding probably to the formula:

l C aHg-S aNa as meaning 0 or a Whole number 1, 2, or 3,

' this dye being obtainable by a slight reduction of 1, 4-di(4-nitr0benzoy1amin0)-benzene-EZ-sulfonic acid, by diazotizing the product obtained, and by coupling it With i 1- (sulfophenyl) -3-methy1-5-pyrazo1one.

In testimony whereof, I affix my signature.

WERNER LANGE. 

